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DNA molecules can be concentrated in a narrow region of a nanochannel when driven electrokinetically in submillimolar salt solutions. Transport experiments and theoretical modeling reveal the interplay of electrophoresis, electro-osmosis, and the unique statistical properties of confined polymers that lead to DNA aggregation. A finite conductance through the bulk of the device also plays a crucial role by influencing the electric fields in the nanochannel. We build on this understanding by demonstrating how a nanofluidic device with integrated electrodes can preconcentrate DNA at selected locations and at physiological salt concentrations that are relevant to lab-on-a-chip applications.

We report on the efficiency of electrical power generation in individual rectangular nanochannels by means of streaming currents, the pressure-driven transport of counterions in the electrical double layer. Our experimental study as a function of channel height and salt concentration reveals that the highest efficiency occurs when double layers overlap, which corresponds to nanoscale fluidic channels filled with aqueous solutions of low ionic strength. The highest efficiency of approximately 3% was found for a 75 nm high channel, the smallest channel measured. The data are well described by Poisson-Boltzmann theory with an additional electrical conductance of the Stern layer.

The pressure-driven transport of individual DNA molecules in 175-nm to 3.8-microm high silica channels was studied by fluorescence microscopy. Two distinct transport regimes were observed. The pressure-driven mobility of DNA increased with molecular length in channels higher than a few times the molecular radius of gyration, whereas DNA mobility was practically independent of molecular length in thin channels. In addition, both the Taylor dispersion and the self-diffusion of DNA molecules decreased significantly in confined channels in accordance with scaling relationships. These transport properties, which reflect the statistical nature of DNA polymer coils, may be of interest in the development of "lab-on-a-chip" technologies.

We theoretically evaluate the prospect of using electrokinetic phenomena to convert hydrostatic energy to electrical power. An expression is derived for the energy conversion efficiency of a two-terminal fluidic device in terms of its linear electrokinetic response properties. For a slitlike nanochannel of constant surface charge density, we predict that the maximum energy conversion efficiency occurs at low salt concentrations. An analytic expression for the regime of strong double-layer overlap reveals that the efficiency depends only on the ratio of the channel height to the Gouy-Chapman length, and the product of the viscosity and the counterion mobility. We estimate that an electrokinetic energy conversion device could achieve a maximum efficiency of 12% for simple monovalent ions in aqueous solution.

We report charge inversion, the sign reversal of the effective surface charge in the presence of multivalent counterions, for the biologically relevant regimes of divalent ions and mixtures of monovalent and multivalent ions. Using streaming currents, the pressure-driven transport of countercharges in the diffuse layer, we find that charge inversion occurs in rectangular silica nanochannels at high concentrations of divalent ions. Strong monovalent screening is found to cancel charge inversion, restoring the original surface charge polarity. An analytical model based on ion correlations successfully describes our observations.

We report measurements of the streaming current, an electrical current generated by a pressure-driven liquid flow, in individual rectangular silica nanochannels down to 70 nm in height. The streaming current is observed to be proportional to the pressure gradient and increases with the channel height. As a function of salt concentration, it is approximately constant below approximately 10 mM, whereas it strongly decreases at higher salt. Changing the sign of the surface charge is found to reverse the streaming current. The data are best modeled using a nonlinear Poisson-Boltzmann theory that includes the salt-dependent hydration state of the silica surface.